JPH02115275A - Offset printing method and offset printing ink - Google Patents

Abstract

PURPOSE: To provide printing ink having a high gloss, luster and color intensity and satisfactory stability by using a specified ester group-contained pyridone azo dye as the coloring agent component for offset printing ink.

CONSTITUTION: This ester group-contained pyridone azo dye is obtained by esterifying a hydroxyl-contained pyridine azo dye represented by the formula I with a 30-60C di- and/or tricarboxylic acid and, if proper, with the other mono- and/or dicarboxylic acid, and, as occasion demands, esterifying the carboxyl group possibly still present in the esterified product with mono- or polyol. In the formula I, R is the formula or the like; R¹ is the formula III or the like; D¹ is a residue of diazo component; L is the formula TV, Q is -O-, -S- or the like; M is (substituted) hydrocarbon group; T is aliphatic or araliphatic group; (n), (p) are 0, 1, 2 or 3, and n+p is 1, 2 or 3.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to offset printing methods and offset printing inks.

German Patent Application No. 3,600,387 discloses a halftone intaglio printing process and a halftone intaglio printing ink, in which esterification products of pyridine azo dyes are used. This publication does not mention anything that the esterification products of pyridine azo dyes are also suitable for offset printing; offset printing, in contrast to halftone intaglio printing, is a lithographic printing process and is chemically based. The amount of printing ink that is used is the one that is used. In particular, one could not have expected that the dyes used according to the invention would be highly compatible with the components of offset printing inks.

The present invention is based on the formula (wherein R is (HO), -D- or T-(OH)n, R1 is (HO), -T'- or D, D' is a residue of a diazo component). , and B may be substituted, and Q is -o--s--so
,--c.

CXH! X (X is 1.2.3.4.5.6) Preferably -CHx CH2CHx-M represents a substituted or unsubstituted hydrocarbon group, and its C
The chain may be interrupted by - or more non-adjacent O atoms, T, T' represent an aliphatic or aliphatic group, which can be interrupted by - or more OH atoms. and m, , n, o, p are 0
．． 1, 2 or 3, provided that the sum of m+p or n+o or n+p is 1.2 or 3),
C3°~C,. - esterification with di- and/or tricarboxylic acids and, if appropriate, other heptano- and/or dicarboxylic acids, and optionally converting the carboxyl groups that may still be present in the esterified product to The present invention relates to an offset printing method characterized in that it uses a pyridone azo dye which is esterified with a polyol and thereby dowels the ester groups obtained.

Preferred hydroxyl-containing pyridone azo dyes have the formula: where 4% r is 0, l, 2.3, and q+
r shall be l, 2 or 3), (wherein s,
t is 0.1, 2.3, provided that S+t is 1.2 or 3).

Particularly preferred are hydroxyl-containing dyes of formulas 1 to 2 having - or more of the structural elements listed below.

1, D represents a phenyl group, which can be substituted or unsubstituted C3-C1, regardless of the number of OH groups.
1 alkyl, C1-CI□alkenyl, cyclohexyl, cyclohexenyl, cyclopentyl, benzyl, phenylisopropyl, CI.

Br, halogens such as F, Cl-01, alkoxy, substituted or unsubstituted phenoxy, -CN,
CF, -NO3, substituted or unsubstituted Cl-C1, alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, substituted or unsubstituted benzylsulfonyl, substituted or unsubstituted phenoxysulfonyl, 1-4 selected from the system consisting of substituted or unsubstituted phenylsulfonyloxy, substituted or unsubstituted C3-C18 alkoxycarbonyl, benzyloxycarbonyl, 2-phenylethyloxycarbonyl and cyclohexyloxycarbonyl It can have substituents.

CI=CI! Alkyl, C1-C1, alkoxy, Cl
The alkyl group in -C1, alkylsulfonyl, Cl-CI8 alkoxycarbonyl is, for example, -08% C
1-C1, alkoxy, formula T''-(CH.

CHzO)a (where T2 is Cl"" CI@alkoxy, c2~C□, alkenyloxy or substituted or unsubstituted phenoxy and a is 1 to 6), or -CN can be replaced by

The phenyl group in phenoxy, phenylsulfonyl, phenoxysulfonyl, phenylsulfonyloxy and phenylsulfonyl can be substituted with halogens such as, for example, C, -C, alkyl, cyclohexyl, phenyl, phenylisopropyl or CI and Br.

Examples of (HO)m-D- or (HO)q-D- are: phenyl, o-lm- and p-methylphenyl, 0- and p-ethylphenyl.

2.3- 3.4- 2.4- and 2,5-dimethylphenyl, 〇- and p-isopropylphenyl, 2-methyl-5-isopropylphenyl, 4-1-butylphenyl, 4-sec-butylphenyl , 〇- and p-dodecylaniline (where the dodecyl group is linear or branched)
, 4-cyclohexylphenyl, 4-cyclohexyl-
2-methylphenyl, 4-(1-cyclohexene-1-
yl)-phenyl, 4-(2-phenyl-isopropyl)-phenyl, o-, m- and p-chlorophenyl, 2.3- 2.4- 2.5- and 3.4-dichlorophenyl, 510Rho2 -Methylphenyl, 4-chloro-2-methylphenyl, 3-chloro-2-methylphenyl, 2-chloro-5-methylphenyl, 4-10rho3
-methylphenyl, 3chloro-4-methylphenyl, 2
-chloro-3゜4-dimethylphenyl, 5-chloro-2
, 4-dimethylphenyl, 4-chloro-2,5-dimethylphenyl, o-lm- and p-nitrophenyl, 2-
10 rho 4-nitrophenyl, 4-10 rho 2-nitrophenyl, 2-methyl-4-nitrophenyl, 4-methyl-2-nitrophenyl, 4-ituprobyl-2-nitrophenyl, 4-t -7'thyl-2-nitrophenyl,
4-cyclohexyl-2-nitrophenyl, 0-lm-
and p-methoxyphenyl, 2-ethoxy- and 4-ethoxyphenyl, 2- and 4-phenoxyphenyl, 2
(2-methoxyphenoxy)-phenyl, 5'IC'rho 2-) l-xyphenyl, 510 rho 2-phenoxyphenyl, 5-chloro-2-(4-chlorophenoxy)-phenyl, 2-methoxy-4-nitro phenyl, 4
-methoxy-2-nitrophenyl, 4-chloro-2,5
-'; Methoxyphenyl, 2-methoxy-5-phenylsulfonylphenyl, 2-methoxy-5-(benzylsulfonyl)-phenyl, 2- and 4-(4-t-butylphenoxysulfonyl]-phenyl, 2- and 4 -(4
-phenylphenoxysulfonyl)-phenyl, 2- and 4- (2-methoxycarbonyl)-phenyl, 2-
and 4-(2-ethyloxycarbonyl)-phenyl, 2- and 4-benzyloxycarbonylphenyl, 2- and 4-(2-phenoxyethoxycarbonyl)-phenyl, 2- and 4-(2-hydroxyethoxy )-phenyl, 4-(2,3-dihydroxypropoxy)-phenyl, 4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-7-enyl, 2-
and 4-(2-hydroxyethoxycarbonyl)-phenyl.

2.Dl is the same as above 1. has the meaning of D given in
shall be independent of each other. (OH).

Examples of pi- or (OH), -D'- are the above 1
, (HO), -D- and (HO), -D-.

unsubstituted or 01-C4 alkyl, C4-C
, alkoxy, halogen (c+, Br) and nitro.

4. If 0 is O, TI is 01-C22 alkyl,
C2~C! 2 alkenyl, C3-C7 cycloalkyl,
Benzyl, 7-enethyl or formula T”-(CH2CH20
)b CHl CH2- and T”-(CH.

CHz O) b -CHt CHz CH2- group, where T2 is CI"" C+a alkoxy,
C1-C1l alkenyloxy or substituted or unsubstituted phenoxy, and b is O-
Hail 6.

Examples are: methyl, ethyl, n- and isopropyl, allyl, n- and impentyl, neopentyl, n-
Hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, decyl, dodecyl, palmityl, stearyl, oleyl, benzyl, -CH, CHt OCHs,
CH2CHz OC2H-CH, CHICH, ○(C
HJsCHs, -CH,CH2CHt OCHx CH
(C2Hs) CHz CHx CHx CHl,
CHx CH2CH20(CHx) 1□CH,,C
H2CHx OCH2CH20CHs, CH2CH!
CH20CH2CHz O(CHz) 3CH3,C
Hxc HxOCsl 5, CHx C
H2CH20C, H-CHx CHx CHx OC
H2CHx OC,H,.

5. If S is 0, T1 is 4. above. It has a meaning given to it.

6. If t is 0, T is 4. above. have the meanings given for TI within, but are mutually independent of, the meanings given for TI.

7. If 0 is greater than 0, T1 represents a C8-C2 alkyl group, which can be interrupted by 1 to 6 zero atoms; examples of corresponding hydroxyl groups are: -C1(,CH,OH.

CH2CH2CH20H--CH2CH(OH) CH
l, -CH,CH(OH)CH2Csummer(3,C(CH
3) 2CH! OH1CHz CHz CH(OH)
CHs, CH2CHz CH2CH! OH, CHx
CHx OCH, CH20Hl CHtc Hx (O
CHzc H2)-OH(p-1-5), -CH2C
H, CH20CH2CH, OH, -CH, CH2CH2
(ocHzcHz).

OH(q-1-3), -CH20H2CH2O(CH
z)<OH, CHxCHxCHz0(CHz)aoH,
-CH2CH2C: HzOCHxCH2CH(CHl
)CH! CH20H--CHz (: H(OH)
CH20H-8, if S is greater than 0, TI
has the meaning given in Section 7 above.

9. If t is greater than 0, then T in 74 above
have the meaning given for 1, but are independent of each other.

10, M represents a C1-C2° hydrocarbon radical, which can be interrupted by 1-7 O atoms. Examples of suitable groups M are: CH2CH2CHx CHz
CH! CH2CH2CHz CH2CH2C
H2CHt CHz CHx -CH2CHlCH,C
H, CHICH, --CH2CH2(OCHxc Hri, --(u-1,2,3,4,5,6),CHxCH
xCHz (OCHzCHz), 0CHzCHICH,
-(V= 1, 2.3.4.5.6), CHzCHxC
HaO(CHz) 40 CH2CHzCH, - 11.9 is l.

12. r is 1.

13.8 is l.

14, t is l.

These structural features 1. ~14. Some combinations of lead to particularly preferred hydroxyl-containing pyridone azo dyes, examples of which are as follows: I1.4; 1.7; 11.12
;IO, Il, I2; 3.5.6; 3.5.9;
3.5. l 4.3.6.8.

3.6. l 3 ; 3.8.9 ; 3.8. l 3
; 3.8.14; 3.9. l 3 ; 3.9. l
4; 3.13.14; 5.6.14; 5.9
．． l4; 6.8.13:8.9. l3;
8.9. l 4 ; 8.13.14.

9.13.14 ; 3.8.9°l 3.13° Preference is given to the use of dyes of formula (V): (wherein D!
represents a phenyl group, which is e.g.
01-C1, alkylcarbonyl such as 2-ethylhexylcarbonyl, Cl-Cl! Alkoxycarbonyl e.g. n-butoxycarbonyl, halogen e.g. Eva CI, B
r, can be substituted with one or two substituents from the system consisting of phenylsulfonyloxy, and HO-T'~ is -CHz CH20H, -CH2CH,
CH,OH, -cH2CHzOCHzCH,OH or -C(CH3)zc HIOH).

Dyes of the formula I-■ are known or can be prepared analogously to processes known from the literature (for example German Patent Application No. 2,216,207, German Patent No. 3,111).
．． No. 648, same No. 3. O12,863, same No. 2,15
2,53 [see No. 3, U.S. Pat. No. 4,476.318, European Patent Application No. 211.326].

C30-C60- used for esterification of dye I-■
The di- or tricarboxylic acids are preferably dimeric and/or trimeric acids or their hydrogenation products known from the literature (for example U. E
ncyclop7idie der Technisc
hen Chemie), 4th edition, vol. 10, p. 141,
7 Verlag Hemi Weinheim (VerlagC
Hemie Wein hsim) I 979; Kirk-Othraer, E.
ncyclopedia of chemical
Technology) 3rd edition, 7 volumes, 768 pages, John Riley Society and Sons, New York (J o
hn Wiley and 5ons, New Yo
R5mpp Chemie-Lexikon, F.rk) 1979;
rank'scheVerlagungshand
Lung, Stuttgart) 1 98 1.
8th edition, vol. 2, p. 964). They are preferably 3
It is a technical grade mixture containing 0-90% by weight of dimer and 70-10% by weight of trimer and a small amount of monobasic carboxylic acid. Dimers are preferably acyclic and/or cyclic C3,-dicarboxylic acids and trimers are preferably C64-tricarboxylic acids. Dimeric and trimeric acids can be obtained by oligomerization of unsaturated fatty acids, such as tall oil fatty acids, oleic acid, elaidic acid, liluic acid.

The above-mentioned hydroxyl-containing polyazo dye and C1゜~
C. In addition to the di- or tricarboxylic acids, further mono- and polyalcohols and heptano- and polycarboxylic acids can additionally be present in the esterification process and incorporated into the corresponding esters.

Examples of suitable monools are methanol, C1-C1 alkanols such as ethanol and higher saturated or unsaturated linear or branched fatty alcohols, preferably saturated or unsaturated C1-C1 fatty alcohols, or Fatty alcohol is a reaction product of C1° to C0 fatty acids or resin acids and ethylene or propylene oxide, and is used, for example, as an emulsifier and a dispersant.

Additionally, reaction products of benzyl alcohol or phenol with ethylene or propylene oxide are suitable. In particular, the following monools are used: diethylene glycol 7-methyl ether, benzyl alcohol, 2-phenoxyethanol, oleyl alcohol, the reaction product of 1 mole of dodecyl alcohol with 3 moles of ethylene oxide, and 2-(2-hydroxyethoxy)-biphenyl. It is preferable.

Examples of suitable diols or polyols include C2-C3,
- di- or polyols, such as 1, 2-1,3- and 1,4-butanediol, neopentyl glycol, 1
．． 6- and 2,5-hexanediol, 3-methyl-1
, 5-bentanediol, 2-methyl-2-propyl-
1,3-propanediol, octanediol (e.g. technical grade mixture), trimethyl-1,6-hexanediol (e.g. mixture), 1,12-octadecanediol, 1. i, l-) Limethylolethane, 1, l,
1-) Limethylolpropane, ethylene glycol, propylene glycol, l,4-cyclohexanediol, 1,4-cyclohexane dimetatool, 2,2-bis(4-hydroxycyclohexyl)-propane, bis(
hydroxymethyl) tricyclodecane (“TCD diol”) and reaction mixtures of these compounds with ethylene or propylene oxide. Other preferred hydroxy compounds are C1-C1,-di- or polyglycols having 3 to 20 ethylene oxide units, C1-C1,-di- or polyglycols having 3 to 20 propylene oxide units and mixed polymers from ethylene oxide and propylene oxide.
Reaction products of 6-C1,-di- or polyglycols and diphenols with ethylene oxide or propylene oxide, such as 1,4-bis(2-hydroxyethoxy)benzene and 2,2-bis(4-(2- hydroxyethoxy)phenyl) to propane.

Particular preference is given to using the following di- or polyols: tetraethylene glycol, 2,2-dimethyl-1,
3-propanediol, l, 4-bis(2-hydroxyethoxy)benzene, trimethylolpropane, 2.2
-bis[4-(2-hydroxyethoxy)phenyl 1
Cyclohexane.

Examples of suitable mono- or polycarboxylic acids which can be incorporated into the oligomeric esters formed during the esterification process are saturated or unsaturated C,O-C0 fatty acids,
Preferably C, to C1 dicarboxylic acids, such as speric acid, azelaic acid, sebacic acid, dodecanedioic acid, dodecenylsuccinic acid, hexahydrophthalic acid,
They are tetrahydrophthalic acid and 4-methylhexahydrophthalic acid.

In the above esterification, it is also possible to use compounds that contain not only carboxyl groups but also aliphatic hydroxyl groups and thus can act on chain extension. These are especially C1~C! 2-hydroxycarboxylic acids, such as glycolic acid, lactic acid, 3-hydroxypropanoic acid, ε-hydroxycaproic acid, ricinoleic acid, hydroxystearic acid, or, if appropriate, lactones, oligomers or polymers of these compounds.

In the esterification, the amounts of dimer and trimer acids chosen are such that the ratio of carboxyl equivalents of the dimer and trimer acids to hydroxyl group equivalents of the pyridone azo dye is preferably at least 0.5:l; Preferably at least 0.8:1 and particularly preferably at least 1:1 and at most 8:11
Preferably at most 6:11, particularly preferably at most 4
: is the amount that is 1. The amount of pyridone azo dye based on the total weight of the esterified product without solvent is at least 10
% should be at most 70%, preferably between 15% and 50%.

In the esterification, the hydroxyl- and carboxyl-containing components to be esterified are used in the simplest case in equivalent amounts. However, the use of excessive amounts of carboxyl-containing components may lead to problems, especially in cases where the hydroxyl-containing pyridone azo dyes have low solubility and are converted into soluble compounds only after esterification.
It can be advantageous. Within the limits mentioned above, the relative amounts of the components used can be varied widely and - by appropriate selection of the ratio of functional to difunctional components, influence the molecular weight of the product compound and thus prepared therefrom. It is possible to influence the viscosity of the printing ink and adjust it to the desired value.

Esterification itself is a conventional method, for example 7 Ubben-Weil,
Methoden der Organizien Chemie, Georg Cieme Verlag, Stuttgart (Houb
en-Weyl, Methoden der org
anischelIChemie, Georg Th
ieme Verlag, Stuttgart),
It can be carried out by the method described in 4th edition, volume 1, pages 516 et seq., 1952.

Regarding the esterification of hydroxyl-containing pyridone azo dyes see, for example, European Patent Application No. 211.326.

Thus, for example, the components can be heated in a suitable solvent in the presence of an acid catalyst and the water produced can be removed azeotropically. Examples of acid catalysts are sulfuric acid, hydrochloric acid, chlorosulfonic acid, phosphoric acid, methane-, ethane- and butanesulfonic acids, benzene-toluene- and dodecylbenzenesulfonic acids, naphthalene-1- and -2-sulfonic acids and acid exchangers. It is resin. Examples of suitable solvents are cyclohexane, toluene and mineral oils, which are also used in the preparation of offset printing inks, and mixtures of these solvents.

After the reaction is complete, the solvent can be removed by distillation, if necessary; the catalyst can remain in the product or can be washed out with water or neutralized with a suitable base, such as a fatty amine.

The esterification product is an oily or resinous substance, which can be easily incorporated into a conventional offset varnish, for example by mixing with a high-speed stirrer and, if appropriate, with mild heating. .

The esterified pyridone azo dyes according to the invention are suitable for dyeing all types of offset printing varnishes, such as varnishes of offset sheet printing inks and rotary offset printing inks and rapid set printing inks. They can completely or partially replace the pigments normally used to dye offset printing inks as well as the resins normally used in the preparation of varnishes. The amount of esterification product according to the invention relative to the total weight of the offset varnish can therefore vary within a wide range and is between about 1% and about 60%, preferably between about 5% and about 40%.
It can be between.

The invention further comprises a colorant (mixture), a varnish (binder) and, if appropriate, additives, the colorant (mixture) containing at least one pyridone azo dye containing ester groups of the type described above. An offset printing ink comprising:

Preferably, the printing ink contains 1 to 60% by weight with respect to the varnish.
colorant (mixture).

Particularly preferably, the printing ink contains from 5 to 40% by weight of colorant (mixture) with respect to the varnish.

In the printing ink according to the invention, the colorant preferably consists of an ester group-containing pyridone azo dye of the type described above. However, it may also be advantageous to use these ester group-containing pyridone azo dyes together with customary printing ink pigments or carbon black. The ester group-containing pyridone azo dyes used according to the invention are completely compatible with conventional pigment-based offset printing inks, so that they can be present in any weight ratio with respect to the pigment.

Naturally, the printing inks according to the invention can additionally contain, in addition to the ester group-containing pyridone azo dyes, other dyes and, if appropriate, printing ink pigments.

Offset printing ink varnishes usually contain a mixture of hard resins, mineral oils, alkyd resins and/or castor oil, the amount of hard resin generally being less than or equal to 45% by weight with respect to the printing ink.

Examples of suitable additives are desiccant agents, anti-delaminating agents, flow improvers, gelling and drawing agents and the like.

An example of the composition of an offset printing ink is as follows: 15-35% by weight colorant (ester group-containing pyridone azo dye), 10-60% by weight mineral oil, 1-10% by weight long-chain oil alkyd resin 0 ~10% by weight titanium dioxide, 0
~5% by weight of a thickener such as one based on montmorillonite, 10-30% by weight of a hydrocarbon resin, the sum of the components being 100% by weight.

The use of the ester group-containing pyridone azo dyes described above provides offset printing inks with high gloss, high gloss and high color strength. Pyridone azo dyes containing ester groups have good solubility in printing inks, so that the dispersion step required when using pigments can be omitted. This printing ink has good stability.

Examples Example 1 102.7 g (0.3 mol) of dye of the formula %, obtained by a conventional method by diazotization and coupling, acid value 195
Pribol 101O (Prip
oll O10) 243.6g, toluene 400m (
2 and 2 g of methanesulfonic acid are heated to reflux for 1 hour and the water formed during esterification is removed in a water separator.

Next, 24.8 g of 2-phenoxyethanol (0,1
8 mol) and pentaglycol (2,2-dimethyl-1
, 3-propanediol) are added and the mixture is heated for a further 4 hours in a water separator. The clear solution obtained is evaporated and residual toluene is removed at water pump pressure at a bath temperature of 90-100°C. resin 3
83 g are obtained, which becomes viscous on heating and solidifies in the form of a wax on cooling.

The thus obtained colored resin 269 was mixed with Pioneer-6625 (Pionier 662) using a high-speed stirrer.
5) (Hansen and Rosenthal)
high viscosity mineral oil (from Rosenthal) 22g
, 3 g refined castor oil (crude castor oil), 5 g Alkydal L 67 (alkyd resin from Bayer), PKWF30/30
(Johann HaHer)
12 g (mineral oil from man), Bayer Titanium RFDI
(Byertitan RF DI) (titanium dioxide from Bayer AG) 5 g, bentone 38 (Be
ntone 38)
2-5 g of thickeners based on organic derivatives of morillonite from one -Chenie), and Set-alin MK 231
(Resin company Synthesis B, V.

24.5 g of hydrocarbon resin (from SynLhese B, V, ) are stirred into a mixture. This is a printing ink 10 highly suitable for rotary offset printing
Give 0g.

In a manner similar to that described in Example 1 above, the pyridone azo dyes listed in Table 1 having the following general formula were treated with the amounts of dimer and trimer acids listed in Table 2 and the alcohols listed therein. Pigmented resins and offset printing inks are obtained when esterified in amounts: Table 2 Column C shows the amount of dimer or trimer acid used per mole of dye in equivalents of carboxyl groups.

Column A shows the amount of -functional alcohol used per mole of dye in moles.

Column D shows the amount of polyfunctional alcohol used per mole of dye in moles.

Pripol 1017 and 1010 are dimer acids and Pripol 1040 and 1049 are trimer acids and are from Unikema.

38.2 g (0.05 mol) of L-mudan-style yellow dye, Bripol 1
87g of 010 and 19°4z of benzyl alcohol
(0.18 mol) is esterified as described in Example I in 150 mf2 of toluene with addition of 1 g of methanesulfonic acid. The mixture was also concentrated to give a yellow resin 145.19 which is highly suitable for incorporation into offset printing inks.

Example 29 114.6 g (0.15 mol) of the same dye as Example 2
Esterification was performed in the same manner as in 4 using 226.29 of Pripol 1010, 11.39 (0.04 mol) of oleic acid and 58.49 (0.54 mol) of benzyl alcohol to obtain 408.7 g of colored resin. It is also suitable for use in offset printing inks.

Physical data for examples Example number λmax (nm) l　　　　　426 Patent applicant: Bayer Akchengesellschaft Representative patent attorney

Claims (1)

[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R represents (HO)_m-D- or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R ^1 represents (HO)＿■-T^1- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, D and D^1 represent the residues of the diazo component, and L represents ▲mathematical formulas, chemical formulas, tables, etc. represents ▼, where the rings denoted by A and B can be substituted, and Q is -O-
, -S-, -SO_2-, -CO-, -C_XH_2_
X-, (X is 1, 2, 3, 4, 5, 6) or ▲ formula,
There are chemical formulas, tables, etc.▼, M represents a substituted or unsubstituted hydrocarbon group, and the C chain can be interrupted by - or more non-adjacent O atoms. , T, T^1 represent an aliphatic or aliphatic group, which may be interrupted by - or more O atoms, m, n, o, p are 0
, 1, 2 or 3, provided that the sum of m+o or m+p or n+o or n+p is 1, 2 or 3).
~C_■_■-di- and/or tricarboxylic acid and
If appropriate, it is obtained by esterification with other mono- and/or dicarboxylic acids and, if desired, by esterification of the carboxyl groups that may still be present in the esterification product with mono- or polyols. An offset printing method characterized by using a pyridone azo dye containing an ester group. 2. It is characterized by using an ester group-containing pyridone azo dye obtained by esterifying the dye of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II)
An offset printing method according to claim 1. 3. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, q and r represent 0, 1, 2, 3, but q +
Offset printing according to claim 1, characterized in that an ester group-containing pyridone azo dye obtained by esterifying a dye (r is 1, 2 or 3) is used. Law. 4. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, s and t represent 0, 1, 2, 3, but s +
The offset printing method according to claim 1, characterized in that an ester group-containing pyridone azo dye obtained by esterifying a dye (t is 1, 2 or 3) is used. 5.Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, D^2 represents a phenyl group, which is, for example, C_1~C_1_2 alkyl, C_1~C_1_2 alkoxy, C_1~C_1_2 alkylcarbonyl, C_
1 to C_1_2 may be substituted with one or two substituents selected from the group consisting of alkoxycarbonyl, halogen, phenylsulfonyloxy,
And HO-T^2- is -CH_2CH_2OH, -CH_2
CH_2CH_2OH, -CH_2CH_2OCH_2
CH_2OH or -C(CH_3)_2CH_2OH
2. The offset printing method according to claim 1, characterized in that an ester group-containing pyridone azo dye obtained by esterifying a dye (representing the above) is used. 6. The offset according to any one of claims 1 to 5, characterized in that an ester group-containing pyridone azo dye obtained by esterification with a dimer and/or trimer acid is used. Printing method. 7. Colorants (mixtures), varnishes and, if appropriate,
An offset printing ink containing an additive, wherein the colorant (mixture) contains at least one of the ester group-containing pyridone azo dyes according to any one of claims 1 to 6. 8. The offset printing ink according to claim 7, wherein the colorant (mixture) is comprised of the ester group-containing pyridone azo dye according to any one of claims 1 to 6. 9. Offset printing ink according to claim 7 or 8, characterized in that it contains from 1 to 60% by weight of a colorant (mixture) with respect to the varnish. 10. Colorant (mixture) in an amount of 5 to 40% by weight with respect to the varnish
The offset printing ink according to claim 7 or 8, characterized in that it contains: